Tris(1, 3, 2-oxazaborolidino) borazoles, tris-(benzo-1, 3, 2-oxazaborolo)borazoles, and a method for their preparation



Hi -Ti in l3 inn n Y 3,045,038 TRIS(1,3,2-OXAZABOROLIDINO)BORAZOLES, TRIS- 3,045,038 ?atented July 17, 1962 selected from the group consisting of ethanolamines having the general formula (BENZO-1,3,2-OXAZABOROLO)BORAZOLES, AND R A METHOD FOR THEIR PREPARATION Robert J. Brotherton, Fullerton, George W. Willcockson, 5

Anaheim, and Howard Steinberg, Fullerton, Calif., as- R-C-NH: signors to United States Borax & Chemical Corporation, Los Angeles, Calif., a corporation of Nevada No Drawing. Filed July 22, 1959, Ser. No. 828,703 and o-aminophenols having the general formula 6 Claims. (Cl. 260-462) 10 X J This invention is a continuation-in-part of our inven- I tion bearing Serial Number 757,211, filed August 26, X 011 1958, and now abandoned.

This invention relates as indicated to borazoles and their preparation and has particular reference to tris- (1,3,2-oxaazaborolidino)borazoles and tris(benzo-1,3,2- X oxaazaborolo)borazoles having N B--O lbOIldS, where R is a substituent selected from the group consist- 'Itis therefore an object of this invention to provide a ing of hydrogen, alkyl radicals of from 1-5 carbon atoms method for the preparation of tris(1,3,2-ox azaand phenyl radicals and X is a substituent selected from borolidinoyborazoles and tris(benzo 1,3,2 oxaazathe g p Consisting of hydrogen, alkyl radicals of from borolo)borazoles. 1-5 carbon atoms, alkoxy radicals of from 1-5 carbon It is another object of this invention to provide as a atoms halogen radicalsnew class of chemical compounds the tris(1,3,2-oxaaza- The Present bol'azolos are conveniently P p y borolidino)borazoles and the tris(benz0-1,3,2-oxaazaheating the foregoing ingredients under reflux and the .bomlo)bor.azoles reaction may be conducted with equimolar quantifies of oth bj t i11 appear as th description ed reactants or an excess of the boric acid ester. Once the T h li h t f th (f i d l d reaction has taken place it is immaterial to the present ends, said invention then comprises the features hereininvention how the resultant crude Product is Separated after fully described and particularly pointed out in the from the reaction mass and purified y f the w llclaims, the following description setting forth in detail known techniques, such as solvent extraction a y certain illustrative embodiments of the invention, these 'liZation pp to the Present inventionbein-g indicative, however, of but a few of the vari It is to be clearly understood that the substituents of ways in which the principle of the invention may be emfilo ethanolannno the o'aminophonol y all be the ployed, same or all different and the o aminophenol may be sub Broadly stated, the present invention comprises as a Stunted in y o or all, or y combination of the new composition of matter a compound selected from 4, 5 and 6 positlonsthe group consisting of nis(1,3,2-oxaazahorolidino) e following equations e yp examples of the borazoles and tris(benzo-1,3,2-oxaazaborolo)borazoles Teaollons of the Present invon'noni represented by the following general formulae: 40 OH 3(RO) B a B NH:

CRr-N NC R: R2C\ 3/0 O-B B N. R2(|3-(|JR: XL QROH and x X B o X C 0-4111, X I X B a Ro ,B com-NH, N

N O HI-OH \2 QROH X X N 0 X X Hg(B-$Hg where R is a substituent selected from the group consist- The following comprises an illustrative list of materials ing of hy g yl radicals of m 5 carbon ms which are useful as reactants in producing the present and phenyl radicals and X is a substituent selected from borazoles. It will be readily seen that the following the group consisting of hydrogen, y radicals f f m is only a partial enumeration of the substituted ethanolcarbon atoms, alkoxy radicals of from 1-5 carbon amines and o-aminophenols and the boric acid esters atoms and halogen radicals, said compounds consisting 0 which are applicable to this invention, and it is to be comof the reaction products of a boric ester derived from 7 pletely understood that it is entirely within the conteman alcohol having from 1-5 carbon atoms and a material plation of this invention to include as reactants all those dim/ 30 5593 1 i f 1 is is. a "1 a if A or, l

materials as defined in the above broadly stated paragraph.

Boric acid esters:

Trimethyl borate Triethyl borate Tri-n-propyl borate Triisopropyl borate Tri-n-butyl borate Tri-t-butyl borate Tri-n-amyl borate Tri-t-amyl borate Ethanolamines:

Ethanolamine l-amino-Z-hydroxpropanc Z-amino-l-hydroxypropane 2-amino-3-hydroxybutane 2-amino-2,3-dimethyl-3-hydroxypropane l-amino-2-hydroxybutane 1-amino-2-eth.yl-2-hydroxybutane 1-amino-2-hydroxy-3-methylbutane l-amino-Z-hydroxyheptane 1-amino-2-hydroxyphenylethane l-amino-l,2-diphenyl-2-hydroxyethane 2-amino-l-hydroxy-l-phenylhexane 2-amino-l-hydroxy-2-methyl-3-phenylpropane 1-amino-3-ethyl-2-hydrQXy-Z-methylbutane Z-amino-l-hydroxy-5-phenyl-3-n-propylpentane (III) o-Aminophenols:

o-Aminophenol 2-amino3-methylphenol 2-amino-3 ,4-dimethylphenol 2-amino-3 ,4,5-trimethylphenol 2-amino-3,4,S,6-tetramethylphenol 2-amino-4-ethylphenol 2-amino-4,5-diethylphenol Z-amino-4,5,6-triethylphenol 2-amino-5-isopropylphenol 2-amino-4-t-butylphenol 2-amino-3-chlorophen0l 2-amino-3,4,5-trichlorophenol 2-amino-3-fiuorophenol 2-amino-3-bromophenol 2-amino-3-isoproxyphenol 2-amino-3,4-diethoxyphenol 2-amino-3,4,5-tri-n-butoxyphenol 2-amino-3chloro-4,S-dimethylphenol 2-amino-4-ethyl-3-methylphenol 2-amino-3-bromo-4-isopropylphenol 2-amino 3-methyl-5-methoxyphenol 2-amino-4-chloro-5-ethoxyphenol 2-amino-3-bromo-4-rnethyl-6-n-propoxyphenol So that the present invention is more clearly understood the following examples are given for illustrative purposes:

Equimolar amounts of o-aminophenol and isopropyl borate were heated in a flask under a fractionating column until substantially all the isopropanol (3 moles per mole of boric acid ester) was evolved (about 16.5 hours). The resulting mass was cooled, filtered and washed with 20 40 petroleum ether. Impurities were removed from the crude product by extraction with benzene, acetone and petroleum ether. The final product had a molecular weight of 338 (theory 351), a chemical analysis of 9.44% B, 60.1% C and 3.52% H, and it decomposed over a range of from 2l0"-280 C. From the assay it will be seen that the final product conforms to the formula (C H NBO) The infrared spectrum of the material was obtained and was consistent with the structure of the trimer. The material was soluble in ethyl acetate, monoglyme, diglyme, sodium hydroxide and hydrochloric acid;

it was slightly soluble in tetrahydrofuran, dioxane and acetone; and was insoluble in benzene, toluene, xylene, ethyl ether, chloroform, acetonitrile, petroleum ether, water and methanol.

Equimolar quantities of ethanolamine and isopropyl borate were heated in xylene under a fractionating column until substantially all the isopropanol (3 moles per mol of boric acid ester) was evolved. Sublimation of the reaction product at 30 mm. yielded a white crystalline solid. Analysis of the product showed it to have the formula (CH CH NBO) Since all of the ingredients as defined above undergo substantially identical reactions and require substantially identical techniques, the foregoing examples are considered sufficient to fully illustrate the present invention.

The new compounds of the present invention will be found to be useful as chemical intermediates; they may be used as fuel additives to improve certain properties of aviation and other gasolines as Well as providing anti sluding properties for diesel fuel. The present borazoles will also be found to be useful as sizing agents for glass fibers and fabrics and as curing catalysts for accelerating the cure of resins and other curable (or potentially curable) materials. The present compounds can also be used to increase the flame resistance of materials into which they have been in cb'fpoiated as a coating or impregnant, e.g., paper, wood and textile materials.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

We, therefore, particularly point out and distinctly claim as our invention:

1. A new composition of matter selected from the group consisting of and where R is selected from the group consisting of hydrogen, alkyl radicals having from 1-5 carbon atoms and phenyl, and X is selected from the group consisting of hydrogen, alkyl radicals having from 1-5 carbon atoms, alkoxy radicals having from 1-5 carbon atoms, and halogen rad- 4. The method of producing a compound selected from the group consisting of substituted and unsubstituted tris- (1,3,2-oxaazaborolidino)borazole and substituted and unsubstituted tris(benzo-1,3,2-oxaazaborolo)borazole which comprises heating under reflux a trialkyl boric acid ester the alkyl group having from l-S carbon atoms with a material selected from the class consisting of ethanolam-ines having the formula R R-(J-OH R-CNH2 1'1 and o-aminophenols having the formula where R is selected from the group consisting of hydrogen, alkyl radicals having from 1-5 carbon atoms and phenyl.

6. The method of producing substituted and unsubstituted tris(benzo-1,3,2 oxaazaborolo)borazole which comprises heating under reflux a trialkyl boric acid ester the alkyl group having from 1-5 carbon atoms with an oaminophenol having the formula where X is selected from the group consisting of hydrogen, alkyl radicals having from l-S carbon atoms, alkoxy radicals having from 1-5 carbon atoms and halogen radicals.

No references cited. 

1. A NEW COMPOSITION OF MATTER SELECTED FROM THE GROUP CONSISTING OF
 4. THE METHOD OF PRODUCING A COMPOUND SELECTED FROM THE GROUP CONSISTING OF SUBSTITUTED AND UNSUBSTITUTED TRIS(1,3,2-OXAAZABOROLIDINO) BORAZOLE AND SUBSTITUTED AND UNSUBSTITUTED TRIS(BENZO-1,3,2-OXAAZABOROLO) BORAZOLE WHICH COMPRISES HEATING UNDER REFLUX A TRIALKYL BORIC ACID ESTER THE ALKYL GROUP HAVING FROM 1-5 CARBON ATOMS WITH A MATERIAL SELECTED FROM THE CLASS CONSISTING OF ETHANOLAMINES HAVING THE FORMULA 